Adhesive composition and method for bonding to rubber

ABSTRACT

An adhesive composition of the present invention comprises (A) a conjugated diene polymer having a weight-average molecular weight of 500 to 100,000 and (B) an electron pair-donating basic compound; or comprises (A) A conjugated diene polymer having a weight-average molecular weight of 500 to 100,000, (C) a compound having in its molecule three or more functional groups selected from the group consisting of acryloyloxy group, methacryloyloxy group and groups represented by the following formula I:  
                 
 
     wherein R 1 , R 2  and m are the same as defined in the specification, and (D) a compound having in its molecule one or two functional groups selected from the group consisting of acryloyloxy group and methacryloyloxy group. At least a part of the surface of an adherend is coated with the adhesive composition to form an adhesive layer. After optionally irradiating the adhesive layer with ultraviolet light or radiation, the vulcanization is preformed while bringing an unvulcanized rubber into press-contact with the adhesive layer, thereby attaining a strong adhesion between the rubber and the adherend. The rubber/adherend composite thus produced is suitably used for the production of rubber-reinforcing materials and rubber articles.

TECHNICAL FIELD

[0001] The present invention relates to an adhesive composition and abonding method using the adhesive composition, and particularly, to anadhesive composition for rubbers, a method for bonding a rubber to anadherend via the adhesive composition by vulcanizing adhesion optionallyafter irradiating the adhesive composition with ultraviolet light, etc.,a rubber-reinforcing material produced by the bonding method, and arubber article using the rubber-reinforcing material.

BACKGROUND ART

[0002] Generally, rubbers have a high elongation and a low elasticmodulus and have been practically made into composites with othermaterials such as plastics to make the best use of their properties. Toproduce such composites advantageously, a rubber and an adherend areintegrally bonded by the vulcanization of the rubber, because such amethod is easily and simply applicable even when the adhesive surface isgeometrically complicated. To ensure an adhesion force, there are knownvarious methods including the surface treatment of plastic adherends,the modification of components of adhesive composition, etc.

[0003] In conventional rubber bonding methods; using an adhesivecomposition, there have been extensively used solvent type adhesivescomprising a rubber-containing adhesive composition and a solvent suchas water and an organic solvent. The solvent is used to make theadhesive composition into liquid state, thereby ensuring a void-freecoating of the adhesive composition on the adherend. To enhance theresistance to cohesive failure of the adhesive composition so as toprevent the adhesive joint from being broken by a stress such as dynamicstrain, the solvent is frequently removed by evaporation, etc. in theadhesion step for hardening the adhesive layer. The adhesive compositionrequiring the removal of the solvent upon hardening the adhesive layerfails to utilize the solvent as an effective component after theadhesive-bonding, and often necessitates a solvent treatment forenvironmental protection. Therefore, the use of a solvent-free adhesivecomposition or an adhesive composition in which the solvent isincorporated into the adhesive layer in the adhesion step for hardeningthe adhesive composition is desired.

[0004] There has been conventionally known a bonding method using, asthe adhesive composition of the above type, an adhesive compositioncontaining a monomer that is polymerizable by the irradiation ofradiation such as ultraviolet light, visible light and electron beam orby the application of external energy such as heat. In this method, theadhesive composition is in a liquid state when applied on the surface ofadherend to thereby minimize adhesive defects due to voids, and theadhesive layer with a network cross-linked structure is formed by thepolymerization of monomer in the adhesive-bonding treatment. Regardingthe method of bonding rubber using the adhesive composition of thistype, Japanese Patent Application Laid-Open No. 55-145768 (DE 2916909C)discloses that: a coating compound comprising at least one liquidhydrocarbon polymer having a double bond and (or), if required, at leastone polyamine derivative is rapidly or completely made into networkstructure by the irradiation of ionizing radiation such as electron beamwithout external heating, thereby ensuring its good adhesion to a rubbersubstrate. It is further described in the document that: the coatingcompound may be applied to a completely vulcanized molded article andthen made into network structure, or alternatively may be applied on acrude mixture not yet made into network structure and then made intonetwork structure simultaneously with the crude mixture. The documentproceeds that: in the latter treatment, if the vulcanization isconducted by the irradiation of electron beam, the use of sulfur as avulcanizing agent and (or) a vulcanization accelerator for making thecrude mixture into network structure can be omitted. The proposed methodrelates to making the rubber component and the adhesive composition intonetwork structure to firmly bond onto rubber, and is characterized thatthe use of sulfur as a vulcanizing agent and (or) a vulcanizationaccelerator can be omitted in making the rubber and the adhesivecomposition into network structure. However, as a result of the studieson the adhesive composition and the bonding method of the presentinvention, the inventors have found that in the case of making theadhesive composition into network structure by the optional irradiationwith irradiation such as ultraviolet light, visible light and electronbeam, when the heating is made while bringing an unvulcanized rubberinto press-contact with the adhesive composition, sulfur migrates fromthe rubber into the adhesive composition, thereby achieving a strongadhesion due to the sulfur-assisted cross-linking reaction.

DISCLOSURE OF INVENTION

[0005] In view of the above circumstances; an object of the presentinvention is to provide a novel adhesive composition capable of creatingan excellent adhesion between a rubber and an adherend simultaneouslywith the vulcanization of the rubber, a bonding method using theadhesive composition, a rubber-reinforcing material having an improvedadhesion between the rubber and the adherend, and a rubber articleproduced by using the rubber-reinforcing material.

[0006] As a result of extensive researches in view of the above object,the inventors have found that a strong and durable rubber-to-adherendadhesion is attained by coating the adherend with a specific adhesivecomposition, and vulcanizing an unvulcanized rubber while bringing itinto press-contact with the adhesive composition optionally afterirradiating the adhesive composition with ultraviolet light orradiation. The present invention has been accomplished on the basis ofthis finding.

[0007] Thus, the present invention provides an adhesive composition forrubbers comprising (A) a conjugated diene polymer having aweight-average molecular weight of 600 to 100,000 and (B) an electronpair-donating basic compound.

[0008] The present invention further provides an ultraviolet- orradiation-curable adhesive composition for rubbers comprising (A) aconjugated diene polymer having a weight-average molecular weight of 500to 100,000, (C) a compound having in its molecule three or morefunctional groups selected from the group consisting of acryloyloxygroup, methacryloyloxy group and terminal groups represented by thefollowing formula I:

[0009] wherein R¹ is C₂-C₅ alkylene group; R² is hydrogen or C₁-C₂ alkylgroup; and m is an integer of 0 to 5, and (D) a compound having in itsmolecule one or two groups selected from the group consisting ofacryloyloxy group and methacryloyloxy group.

[0010] The present invention still further provides a method for bondinga rubber to an adherend via the adhesive composition mentioned above,comprising: coating at least a part of a surface of the adherend withthe adhesive composition to form an adhesive layer, and vulcanizing anunvulcanized rubber while bringing it into press-contact with theadhesive layer, optionally after irradiating the adhesive layer withultraviolet light or radiation.

[0011] The present invention still further provides a rubber-reinforcingmaterial produced by the above method, and a rubber article particularlya tire reinforced by the rubber-reinforcing material.

BRIEF DESCRIPTION OF DRAWINGS

[0012]FIG. 1 is a graph showing a heat-of-reaction curve as measured bya differential scanning calorimeter which shows acceleratedvulcanization of methacrylated polybutadiene as a conjugated dienepolymer by 4-vinylpyridine as an electron pair-donating basic compound.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The first adhesive composition of the present invention comprises(A) a conjugated diene polymer having a weight-average molecular weightof 500 to 100,000 and (B) an electron pair-donating basic compound.

[0014] The upper limit of the weight-average molecular weight (Mw) ofthe component A is not particularly restricted unless the adhesivecomposition shows an excessively high viscosity and becomes difficult tobe processed. However, when exceeding 100,000, the coating of theadhesive composition tends to be difficult. When the Mw is less than500, a sufficient adhesiveness cannot be sometimes atained by thevulcanization of the press-contacted unvulcanized rubber. Consideringthe above, Mw is preferably 500 to 100,000.

[0015] The conjugated diene polymer as the component A may includeconjugated diene homopolymers, conjugated diene copolymers and modifiedpolymers or copolymers thereof. Examples of the conjugated dienemonomers include 1,3-butadiene, isoprene and 1,3-hexadiene, with1,3-butadiene being preferred. The conjugated diene copolymers arepreferably conjugated diene-aromatic vinyl copolymers. The aromaticvinyl monomer may be styrene or α-methylstyrene, with styrene beingpreferred. The conjugated diene polymer preferably contains in its mainmolecular chain units containing a carbon-carbon double bond havinghydrogen at its allyl position so as to provide sites capable of easilyforming cross-link by the cross-linking reaction with sulfur. Examplesof the conjugated diene polymers include polyisoprene, polybutadiene,styrene-butadiene copolymers and isoprene-butadiene copolymers. It ispreferred for the conjugated diene polymer to be in a liquid state at ablending temperature for preparing the adhesive composition andparticularly even at 0° C. or lower in view of good workability andeasiness of the mixing step for preparing the adhesive composition. Itis also preferred to be in a liquid state with a low vapor pressure evenat 50° C. or higher. However, the liquid state of the conjugated dienepolymer at the blending temperature is not critical as long as theconjugated diene polymer presents in a liquid state in the resultantadhesive composition.

[0016] Also usable are modified polymers produced by introducingfunctional groups having a radically-polymerizable unsaturated doublebond into ends of the conjugated diene polymers. Examples of thefunctional groups include vinyl group, acryloyl group, methacryloylgroup, acryloyloxy group, methacryloyloxy group and allyl group.Particularly preferred as the modified polymer are butadiene polymershaving at their ends acryloyl group, methacryloyl group, acryloyloxygroup or methacryloyloxy group. The modified polymers are available ascommercial products or trade samples.

[0017] For example, acrylated polybutadienes produced by introducingacryloyl group (CH₂═CHCO—) into the ends of butadiene polymers areavailable from Osaka Yuki Kagaku Kogyo, Co., Ltd. under the trademark“BAC45” (Mw of polybutadiene moiety: 2,800; viscosity: 3.4 Pa.s;saponification value: about 49). Also, methacrylated polybutadienesrepresented by the following formula:

[0018] are available from Ricon Resins Inc. under the trademarks“RIACRYL3100” (Mw: 5,100; number of methacryloyl(oxy) groups;2/molecular chain), “RIACRYL3500” (Mw: 6,800; number of methacryloylgroups: 9/molecular chain) and “RIACRYL3801” (Mw: 3,200; number ofmethacryloyl(oxy) groups: 8/molecular chain).

[0019] The electron pair-donating basic compound as the component B: mayinclude compounds containing nitrogen atom having a lone pair orcompounds capable of producing compounds having a lone pair by thermaldecomposition.

[0020] Examples of the compounds containing nitrogen atom having a lonepair include amine compounds such as (a) aromatic canines, (b) aldehydeamines, (c) guanidines, (d) thiouric acids, (e) heterocyclic amines and() polymerizable monomers having aliphatic amine residues orheterocyclic amine residues and further having a carbon-carbon doublebond. The aromatic amines (a) may include amino-containing aromaticcompounds such as aniline, m-phenylenediamine and 2,4-toluylenediamine.The aldehyde amines (b) may include n-butylaldehyde aniline. Theguanidines (c) may include diphenylguanidine and di-o-tolylguanidine.The thiouric acids (d) may include thiocarbanilide, diethylthiourea andtetramethylthiourea. The heterocyclic amines (e) may include compoundshaving a nitrogen-containing heterocyclic ring such as pyridine and2-methylimidazole. The polymerizable monomers (I) may include2-vinylpyridine, 4-vinylpyridine, m-(N,N-dimethylamino)styrene,p-(N,N-dimethylamino)styrene, acrylamide, methacrylamide,N-methylacrylamide, N-isopropylacrylamide, N-n-butylacrylamide,N-n-octylacrylamide, N,N-dimethylacrylamide, 1-vinylimidazole,allylamine, 2,5-distyrylpyridine, 2-dimethylaminoethylmethacrylate,N-vinyl-2-pyrrolidone, 2-vinyl-2H-indazole, 4-diisopropylamino-1-butene,trans-2-butene-1,4-diamine, 2-vinyl-4,6-diamino-1,3,5-triazine,4-methyl-5-vinylthiazole, N-vinylformamide,N,N-dimethylaminoethylacrylate, N,N-diethylaminopropylacrylamide,acryloylmorpholine, and N,N-diethylacrylamide.

[0021] In addition to the above compounds, also usable as the compoundscontaining nitrogen atom having a lone pair are (g) aliphatic amines and(h) amine compounds other than the compounds (a) to (g). Examples of thealiphatic noes (g) include aliphatic monoamines such as dibutylamine;diamines such s ethylenediamine; and high-molecular amines such aspolyethylenepolyamine. Examples of the amine compounds on) other thanthe compounds (a) to (g) include substituted amine compounds havingacrylated or methacrylated primary or secondary amino groups.

[0022] Of the compounds (a) to (h) containing nitrogen atom having alone pair, preferred are the compounds (a) to (f), and more preferredare the compounds (e) and (f).

[0023] The compounds capable of producing compounds containing astructure having a lone pair by thermal decomposition are preferablyknown vulcanization accelerators, for example, disulfide compounds suchas tetramethylthiuram disulfide. The compounds capable of producingcompounds containing a structure having a lone pair by thermaldecomposition are preferably decomposed upon vulcanization for adhesionat a vulcanization temperature of 130 to 180° C.

[0024] When vulcanizing the unvulcanized rubber while bringing it intopress-contact with the adhesive lyaer which is formed by coating atleast a part of the surface of the adherend with the adhesivecomposition, the sulfur in the unvulcanized rubber migrates into theadhesive layer to create a strong adhesion between the adherend and therubber because of the co-vulcanization of the component A and the rubbercomponent. The component B catalyzes the reaction between theunsaturated moieties of the component A and the sulfur migrating fromthe unvulcanized rubber. The vulcanization accelerating effect of thecomponent B can be confirmed from the heat-of-reaction curve measured bya differential scanning calorimeter at a temperature rise rate of 5°C./min. A comparative composition comprising a mixture of 100 parts byweight of the component A and 3 parts by weight of sulfur (butcontaining no component B) shows no peak of reaction heat attributableto the vulcanization in a temperature range of 190° C. or lower of itsheat-of-reaction curve. On the contrary, a mixture of 100 parts byweight of the adhesive composition of the present invention and 3 partsby woight of sulfur shows a peak of reaction heat attributable to thevulcanization in a temperature range of 190° C. or lower of itsheat-of-reaction curve. At the reaction temperature of 190° C. or lower,the vulcanization generally proceeds dominantly by a ring openingreaction caused by the vulcanization accelerator or electronpair-donating base rather than by the radical vulcanization. In anadhesive composition containing a component having a relatively acidicend group such as (meth)acryloyl group, the electron pair-donating baseis difficult to participate in the vulcanization. Therefore, theaddition of the electron pair-donating base (component B) is required tofacilitate the vulcanization.

[0025] The donating of electron pair from the electron pair-donatingbase (component B) to the sulfur-based vulcanizing agent such as cyclicsulfur S₈ means occurrence of donor-acceptor interaction. Therefore, theamount of sulfur migrating from the unvulcanized rubber into theadhesive composition vanes depending upon the content of tho electronpair-donating base in the adhesive composition and its basicity againstsulfur. In this regard, the inventors have found that the amount ofmigrating sulfur generally increases with increading amount of theelectron pair-donating base and increasing basicity against sulfur. Whenthe amount of sulfur distributed in the adhesive layer of the adhesivecomposition increases, the amount of sulfur present at a boundarybetween the adhesive layer and the rubber also increases to enhance thebonding by the sulfur vulcanization. Therefore, the addition of theelectron pair-donating base (component B) is required to facilitate themigration of the vulcanizing agent into the adhesive composition.

[0026] The addition amount of the component B varies depending upon theelectron pair-donating capability of the base, and is preferably 0.2 to50 parts by weight based on 100 parts by weight of the component A. Whenless than 0.2 part by weight, the component B fails to show thevulcanization accelerating effect. When more than 50 parts by weight,physical properties of the adhesive composition are deteriorated becauseof excessive vulcanization.

[0027] The adhesive composition may optionally contain the followingcomponent C (30 to 80 parts by weight based on 100 parts by weight ofthe component A) and/or the component D (3 to 60 parts by weight basedon 100 parts by weight of the component A).

[0028] The component (C) is a compound having, per one molecule, threeor more, preferably 3 to 8 functional groups which is cross-linkable bythe irradiation with ultraviolet light or radiation. Examples of thepreferred functional groups include acryloyloxy group, methacryloyloxygroup and functional groups represented by the formula I:

[0029] wherein R¹ is C₂-C₅ alkylene group, preferably ethylene group orpropylene group; R² is hydrogen or C₁-C₃ alkyl group, preferablyhydrogen or methyl group; m is an integer of 0 to 5, preferably 1 to 3,with the groups represented by the formula I being more preferred.Examples of the compounds having three or more acryloyloxy ormethacryloyloxy groups include esters of a tri- or more valentpolyhydric alcohol and acrylic or methacrylic acid. The polyhydricalcohol preferably used may be glycerol, trimethylolethane,trimethylolpropane, diglycerol, pentaerythritol and dipentaerythritol.The compounds having three or more functional groups represented by theformula I are commercially available and exemplified by pentaerythritolpolyethoxyacrylate having the following formula:

[0030] wherein m x a=3 and a+b=3, available from Nippon Kayaku Co., Ltd.under the trademark “KAYARAD TPA-330”; pentaerythritolpolypropoxyacrylate available from Nippon Kayaku Co., Ltd. under thetrademarks “KAYARAD TPA-320” and “KAYARAD TPA-330”; dipentaerythritolpolyacrylate available from Arakawa Kagaku Kogyo Co., Ltd. under thetrademark “BEAMSET 700”; and pentaerythritol polyacrylate available fromArakawa Kagaku Kogyo Co., Ltd. under the trademark “BEAMSET 710.”

[0031] The component (D) serves as a viscosity modifier, and ispreferably a mono- or di-functional liquid compound having one or twofunctional groups which is radically polymerizable by the irradiation ofultraviolet light or radiation, Of these compounds, preferred arepolyoxyalkylene derivatives having one or two acryloyloxy ormethacryloyloxy groups in one molecule. Such viscosity modifiers may becommercially available. Examples of the monofunctional compounds includephenoxypolyethylene glycol monoacrylate represented by the formula:

[0032] wherein n is 4, available from Shin-Nakamura Kagaku Kogyo Co.,Ltd. under the trademarks “AMP-60G” and “APG-400”; tetrahydrofurfurylmonoacrylate available from SARTOMER Inc. under the trademark “SR-285”;and isooctyl monoacrylate available from SARTOMER Inc. under thetrademark “SR-440.” Examples of the difunctional low-molecular compoundsinclude polypropylene glycol diacrylate represented by the formula:

[0033] wherein m+n=7, available from Shin-Nakamura Kagaku Kogyo Co.,Ltd. under the trademark “APG-400”; and polypropylene glycoldimethacrylate available from Shin-Nakamura Kagaku Kogyo Co., Ltd. underthe trademark “9PG.”

[0034] The adhesive composition may also optionally contain anappropriate low-viscosity liquid having a racial reactivity according toprocessing requirements.

[0035] Further, the adhesive composition may optionally contain at leastone additive selected from the group consisting of epoxy compounds,inorganic fillers and high-molecular fillers in a total amount of 10 to40 parts by weight based on 100 parts by weight of the component A.

[0036] The epoxy compounds are cross-linked by heating to impartductility and toughness to the adhesive composition. Examples thereofinclude novolak epoxy resins produced by epoxidating a condensate of aphenol compound and formaldehyde, and novolak phenol resins produced byintroducing an epoxy or (meth)acrylic group into a condensate of aphenol compound and formaldehyde. Commercially available epoxy compoundsare exemplified by epoxy novolak acrylate (trademark “ENA”) and novolakacrylate having epoxy and carboxyl groups (trademark “ENC”) which areavailable from Kagawa Chemical Co., Ltd.

[0037] The inorganic fillers and the high-molecular fillers arepreferably added to reduce production costs of the adhesive composition,simultaneously with imparting ductility and toughness thereto. Examplesof the inorganic fillers include clay, silica, talc, and carbon black.Commercially available clay is exemplified by montmorillonite clayavailable from NANOCOR INC. under the trademarks “Nanomer PGW”, “NanomerPGA”, “Nanomer PGV” and “Nanomer PGN.” Examples of the high-molecularfillers include copolymers of isobutylene and maleic anhydride, modifiedpolybutadienes, and modified acrylonitrile-butadiene copolymers.Commercially available high-molecular fillers are exemplified bycopolymers of isobutylene and maleic anhydride available from KurarayCo., Ltd. under the trademarks “ISOBAN 10”, “ISOBAN 04” and “ISOBAN110”, amine-modified acrylonitrile-butadiene copolymer (trademark “HYCARATBN 1300×16”) and carboxyl-modified acrylonitrile-butadiene copolymer(trademark “HYCAR CTBN 1300×8”) available from Ube Industries, Ltd.

[0038] The second adhesive composition of the present inventioncomprises (A) a conjugated diene polymer having a weight-averagemolecular weight of 500 to 100,000, (C) a compound having in itscolocule three or more functional groups cross-linkable by theirradiation of ultraviolet light or radiation, and (D) a viscositymodifier. The components A, C and D are the same as those mentionedabove. Therefore, the details thereof are omitted here.

[0039] The blending amounts of the components A, C and D are notparticularly restricted as long as a strong bonding force between theadherend and rubber is attained, and preferably 30 to 80 parts by weightfor the components C and 3 to 60 parts by weight for the component Deach based on 100 parts by weight of the component A.

[0040] The second adhesive composition may further contain at least oneadditive selected from the group consisting of epoxy compounds,inorganic fillers, high-molecular fillers and basic compounds in a totalamount of 10 to 40 parts by weight based on 100 parts by weight of thecomponent A. The epoxy compounds, inorganic fillers and high-molecularfillers may be selected from those optionally added to the firstadhesive composition. Also, the basic compounds may be selected fromthose used as the component B in the first adhesive composition.

[0041] In addition, the second adhesive composition preferably containsa pbotoinitiator such as 2,4-diethylthioxanthone (for example, “KAYACUREDETX-S,” trademark, available from Nippon Kayaku Co., Ltd.) and isoamylp-dimethylaminobenzoate (for example, “KAYACURE DMBI,” trademarkavailable from Nippon Kayaku Co., Ltd.) in an amount of 0.1 to 10 partsby weight based on 100 parts by weight of the component A. Further, thesecond adhesive composition may contain sulfur (for example, powderysulfur available from Karuizawa Seisakusho Co., Ltd,), a vulcanizationaccelerator (for example, mercaptobenzothiazole available from FlexysInc. under the trademark “Perkacit MBT PDR-D”, and disulfide availablefrom Akuzo Inc. under the trademark “Lucidol S-50”), or peroxide, eachin an amount of 0.1 to 3 parts by weight based on 100 parts by weight ofthe component A.

[0042] The material of the adherend to be bonded to the rubber is notparticularly restricted, and is preferably thermoplastic resin. Examplesof the thermoplastic resins include polyamides, polyesters, polyolefinssuch as polypropylene and polyethylene, polycarbonates, polyacrylates,styrene resins such as ABS resin, and vinyl chloride resins. Of thesethermoplastic resins, preferred are polyesters having a high mechanicalstrength which are not easily bonded to rubbers by ordinary methods. Theplastic adherend to be used in the present invention may be in any formsuch as film, fibers, non-woven fabric, monofilament cord andmultifilament cord, and may be extrued articles or injection-moldedarticles.

[0043] In the bonding method of the present invention, the adhesivecomposition is applied to at least a part of a surface of the adherend,for example, one surface of a sheet-like adherend, by immersion;brushing, casting, spraying, roll-coating, knife-coating, etc., to forma coating film. The surface of the adherend may be treated in advance byelectron bean, microwave, corona discharge, plasma treatment, etc. Thethickness of the adhesive composition layer is preferably 0.5 to 50 μmand more preferably 1 to 10 μm.

[0044] The adhesive composition layer is then irradiated withultraviolet light or radiation. The radiation may include electron beam,gamma ray, etc., and may be irradiated by known methods. In general theexposure dose is 100 to 3,000 mJ/cm² and the exposure time is 1 to 30 sfor the ultraviolet light irradiation, and the exposure dose is 2 to 50Mad and the exposure time is 0.5 to 30 s for the electron beamirradiation. The adhesive composition is hardened to some extent by theradical reaction induced by the irradiation. The irradiation ofultraviolet light or radiation can be omitted for the first adhesivecomposition. By heating at 140 to 190° C. for 10 to 30 min whilebringing an unvulcanized rubber into press-contact with the adhesivecomposition layer under a pressure of 5 to 50 kgf/cm², co-vulcanizationreaction occurs between the base polymer (component A) of the adhesivecomposition and the rubber, resulting in a strong adhesion between theadhesive composition and the rubber.

[0045] In the bonding method of the present invention, it is preferredto form an undercoat layer (primer layer) on at least a part of thesurface of the adherend, and then form the coating film of the adhesivecomposition thereon. The thickness of the undercoat layer is preferably1 to 10 μm. As the undercoat composition, there may be used knownsuitable adhesives according to the material of the adherend. Althoughnot particularly restricted, the undercoat composition preferablycomprises (E) 100 parts by weight of a compound having a bisphenolbackbone represented by the following formula II:

[0046] wherein R³ and R⁴ are each independently hydrogen or C₁-C₃ alkylgroup, preferably hydrogen or methyl group; and n is an integer of 1 to3, and (F) 5 to 50 parts by weight of a compound having in its moleculethree or more acryloyloxy and/or methacryloyloxy groups.

[0047] The component E preferably has, in addition to the bisphenolbackbone represented by the formula II, an end group represented by thefollowing formula III:

[0048] wherein R⁵ is C₂-C₅ alkylene group, preferably ethylene group;and p is an integer of 1 to 5, preferably 1 to 3.

[0049] The component E may be commercially available as ethoxylatedbisphenol F diactylate represented by the formula:

[0050] wherein m+n=4 (available from Nippon Kayaku Co., Ltd. under thetrademark “KAYARAD R-712”), ethoxylated bisphenol A diacrylate(available from Nippon Kayaku Co., Ltd. under the trademark “KAYARADR-551”), ethoxylated bisphenol A dimethacrylate (available from SARTOMERInc. under the trademarks “SR-348”, “SR-480” and “SR9036”), andethoxylated bisphenol A diacrylate (available from Arakawa Kagaku KogyoCo., Ltd. under the trademark “BEAMSET 750”).

[0051] As the component F, there may be used the same compounds as usedas the component C of the adhesive composition.

[0052] To enhance the strength of the coating film, the undercoatcomposition may contain a conjugated diene polymer selected from thoseas used for the component A of the adhesive composition in an amount of0.5 to 10 parts by weight based on 100 parts by weight of the componentE, and may also contain, if desired, the viscosity modifier and thephotoinitiator mentioned above in amounts of 5 to 30 parts by weight and0.1 to 5 parts by weight, respectively, based on 100 parts by weight ofthe Component E. Further, the undercoat composition may contain astyrene monomer as a radical reaction promoter in an amount of 1 to 20parts by weight based on 100 parts by weight of the component E, Inaddition to the above components, the undercoat composition may furthercontain at least one additive selected from the group consisting of thesame opoxy compounds, inorganic fillers, high-molecular fillers andbasic compounds as described in connection with the adhesive compositionin a total amount of 5 to 10 parts by weight based on 100 parts byweight of the component E.

[0053] The surface of the undercoat layer formed from the abovecomposition is preferably irradiated with ultraviolet light orradiation.

[0054] In a preferred embodiment of the present invention, a compositehaving a laminated structure of adherend/undercoat layer/adhesivecomposition layer/rubber is produced by forming the undercoat layer onthe surface of the adherend; laminating the adhesive composition layeron the undercoat layer; irradiating, if desired, the adhesivecomposition layer with ultraviolet light or radiation; and performingvulcanization while bringing an unvulcanized rubber into press-contact.

[0055] The rubber used in the present invention is not particularlyrestricted. Examples of the rubber include natural rubbers; conjugateddiene synthetic rubbers such as polyisoprene synthetic rubber (IR),polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR),acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR) and butylrubber (IIR); ethylene-propylene copolymer rubber (EPM);ethylene-propylene-diene copolymer rubber (EPDM); and polysiloxanerubbers, with natural rubbers and conjugated diene synthetic rubbersbeing preferred. These rubbers may be used in combination of two ormore.

[0056] The rubber may be vulcanized in the presence of a vulcanizingagent. Examples of the vulcanizing agents include sulfur; thiurampolysulfide compounds such as tetramethylthiuram disulfide anddipentamethylenethiuram tetrasulfide; 4,4-dithiomorpholine; p-quinonedioxim; cyclic sulfur imides; and peroxides, with sulfur beingpreferred.

[0057] The rubber may contain, in addition to the above components,various additives ordinarily used in rubber industries, for example,fillers such as carbon black and silica, vulcanization accelerators suchas aluminum hydroxide, antioxidants and softeners. The rubber may bemade into a composite with particles, fibers and cloths of variousmaterials.

[0058] The present invention is described in more detail by reference tothe following examples. However, it should be noted that the followingexamples are only illustrative and not intended to limit the inventionthereto.

[0059] A composite of a rubber and an adherend was prepared by thefollowing method, and subjected to various tests.

[0060] 1. Polyester Film/Rubber Composite

[0061] An undercoat composition shown in Table 1 was applied onto onesurface of a 100 μm-thick polyethylene terephthalate film (availablefrom Teijin Limited under the trademark “TETRON TYPE-O”) using a filmcoater to form an undercoat layer, which was then irradiated withultraviolet light (for 5 s at an intensity of 500 mJ/cm² and for 10 s atan intensity of 1,000 mJ/cm²) using an ultraviolet irradiation apparatus(“ECS-301G1” available from EYE GRAPHICS Co., Ltd.), or irradiated withelectron beam (exposure dose: 40 or 25 MRad) using an electron beamirradiation apparatus (“ELECTROCURTAIN CB250/15/180L” available from EYEGRAPHICS Co., Ltd.).

[0062] Next, the treated undercoat layer was coated with an adhesivecomposition shown in Table 1 using a film coater to form an adhesivelayer, After ultraviolet irradiation (for 5 s at an intensity of 500mJ/cm² and for 10 s at an intensity of 1,000 mJ/cm²) or electron beamirradiation (exposure dose: 7, 15 or 20 MRad) or without irradiation,the vulcanization was performed under the following conditions to obtaina 80 mm x 80 mm polyester film/rubber composite.

[0063] Unvulcanized Rubber

[0064] thickness: 2.3 mm formulation: shown in the following table.Formulation part by weight Natural rubber 100 Carbon black 40 Stearicacid 2 Petroleum softening agent 2 Zinc white 5 Antioxidant** 1.5N-t-butyl-2-benzothiazolylsulfenamide 1.2 Diphenylguanidine 0.75 Sulfur2.5

[0065] Vulcanization Conditions:

[0066] Contact pressure: 15 kg/cm²

[0067] Vulcanizing temperature: 160° C.

[0068] Vulcanizing time: 20 min

[0069] 2. Polyester Cord/Rubber Composite

[0070] In continuous manner, a polyethylene terephthalate tire cordhaving a twisting structure of 1,500 d/2, a ply twist number of 39turn/10 cm and a cable twist number of 39 turn/10 cm was immersed in theundercoat composition shown in Table 1 and passed between squeeze rollsto remove the excess undercoat composition. Then, the tire cord waspassed through a photo-curing zone of an ultraviolet irradiationapparatus at a speed of 150 cm/min to irradiate the undercoat layer withultraviolet light (for 10 s at an intensity of 1,000 mJ/cm²).

[0071] The obtained tire cord having the ultraviolet-cured undercoatlayer was immersed in the adhesive composition shown in Table 1 andpassed between squeeze rolls to remove the excess adhesive composition.Then, the tire cord was passed through a photo-curing zone of anultraviolet irradiation apparatus at a speed of 150 cm/min to irradiatethe adhesive composition layer with ultraviolet light (for 10 s at anintensity of 1,000 mJ/cm²).

[0072] The adhesive-treated polyester cord was embedded in a 2.3mm-thick unvulcanized rubber having tho formulation as shown in theabove Table, and vulcanized under a pressure of 20 kgf/cm² at 160° C.for 20 min to obtain a polyester cord/rubber composite.

[0073] 3. Nylon Cord/Rubber Composite

[0074] The same procedure as in the production of the polyestercord/rubber composite was repeated except for using a tire cord having atwisting structure of 1,260 d/2, a ply twist number of 39 turn/10 cm anda cable twist number of 39 turn/10 cm and irradiating the undercoatlayer with electron beam (exposure dose: 40 MRad) to obtain a nyloncord/rubber composite.

[0075] 4. Film Peel Test

[0076] The polyester film/rubber composite was cut into 25 mm in widthto prepare a test specimen for peel test.

[0077] The test specimen was tested for peeling between the rubber layerand the polyester film at a peel angle of 180° (T-peel) and a peel rateof 50 mm/min to measure a peel strength. The area ratio of the adheringrubber (rubber adhesion rate) to the surface area of the film afterpeeling was measured to rank the rubber adhesion according to thefollowing table. The results are shown in Table 1. Ranks Rubber adhesionrate Condition of film after peeling A+ — Broken A 100-80% Not broken B 80-60% Not broken C  60-40% Not broken D  40-20% Not broken E  20-0%Not broken

[0078] 5. Cord Tensile Test

[0079] The tire cord was dug out of each of the polyester cord/rubbercomposite and nylon cord/rubber composite, and peeled off from eachcomposite at a rate of 30 cm/min to measure a peel resistance, which wasemployed as the adhesion strength (tension). The area ratio of theadhering rubber to the surface area of the cord after peeling wasmeasured to rank the rubber adhesion according to the following table.The results are shown in Table 1. Ranks Rubber adhesion rate Conditionof cord after peeling A+ — Broken A 100-80% Not broken B  80-60% Notbroken C  60-40% Not broken D  40-20% Not broken E  20-0% Not broken

[0080] 6. Heat-of-Reaction Curve

[0081] The respective adhesive compositions were irradiated withultraviolet light (for 5 s at an intensity of 500 mJ/cm²) to preparefilms. Each film was cut into small pieces and screened by a 30 meshmetallic sieve to obtain each powder. Each 100 parts by weight of powderwas uniformly kneaded with 3 parts by weight of insoluble sulfur (under80 mesh) to prepare each specimen.

[0082] A stainless steel pressure pan containing the specimen was set ina differential scanning calorimeter. The temperature was held at 70° C.at which vulcanization does not initiate for 5 min, and then raized at arate of 5° C./min to measure the heat of reaction (W/g) and prepare aheat-of-reaction curve from the measured results.

[0083] An example of the heat-of-reaction curves thus prepared isillustrated in FIG. 1. The formulation of each specimen is shown below.Formulation of Specimen Adhesive composition (part by weight) ComponentA Component B Sulfur (part by weight)  0% VP 100 0 3  5% VP 95 5 3 10%VP 90 10 3 15% VP 85 15 3 20% VP 80 20 3

[0084] As seen from FIG. 1, the curve for the composition (0% VP)containing no component B (electron pair-donating basic compound:4-vinylpyridine) showed a flat base line with no peak in a temperatureregion of 190° C. or lower, especially 180° C. or lower. In the curvesfor the compositions that were added with the component B, shoulderpeaks (indicated by arrows) attributable to the vulcanization reactionappeared in a temperature region of 120 to 190° C. The inflection pointof each shoulder peak calculated by differential method is shown inTable 1 as the heat-of-reaction peak temperature.

[0085] 7. Migrating Amount of Sulfur (Rubber→Adhesive Composition)

[0086] The polyester film/rubber composite prepared in the mannerdescribed above was cut in the direction perpendicular to the surfacethereof. The cut film was cross-sectionally observed by a scanningelectron microscope coupled with an X-ray analyzer to count thefluorescent X-ray from sulfur in the rubber layer, adhesive layer andfilm layer. The amount of sulfur migrated from the rubber layer into theadhesive layer was evaluated by whether the sulfur content in theadhesive layer is high or low as compared to the average distribution ofsulfur content in the rubber layer.

[0087] 8. Pneumatic Tire

[0088] A polyethylene terephthalate tire cord having a twistingstructure of 1,500 d/2, a ply twist number of 39 turn/10 cm and a cabletwist number of 39 turn/10 cm was immersed in the undercoat compositionshown in Table 1 and passed through squeeze rolls to remove the excessundercoat composition. Then, the tire cord was passed through aphoto-curing zone of an ultraviolet irradiation apparatus at a speed of150 cm/min to irradiate the resultant undercoat layer with ultravioletlight (for 10 s at an intensity of 1,000 mJ/cm²).

[0089] The tire cord having the ultraviolet-cured undercoat layer wasimmersed in the adhesive composition shown in Table 1 and passed throughsqueeze rolls to remove the excess adhesive composition. Then, the tirecord was passed through a photo-curing zone of an ultravioletirradiation apparatus at a speed of 150 cm/min to irradiate theresultant adhesive layer with ultraviolet light (for 10 s at anintensity of 1,000 mJ/cm²), thereby preparing adhesive-treated polyestercords of Comparative Example 14 and Example 37.

[0090] The adhesive-coated polyester cords of Comparative Example 14 andExample 37 were respectively used as a single carcass ply to produce apneumatic radial tire having a size of 155R13.

[0091] 9. Adhesion Strength of Polyester Cord/Rubber Composite afterTire Running

[0092] Each tire of Comparative Example 14 and Example 37 was seated ona rim prescribed in JIS D4202, and mounted to an ordinary passenger carfor running on a flat asphalt road surface at a speed of 30 km/h over 10km (preliminary running). The tire of Example 37 was further run onusual road over 10,000 km. The tenacity (N) of the cord after runningwas measured according to JIS L1017. A sample of 100 mm long in the plycord direction and 25 mm long in the circumferential direction was cutout by a knife from the side portion of each tire. The cord was dug upfrom the sample and peeled off from the side rubber at a speed of 30cm/min to measure the peel resistance (N) which is shown as the adhesionstrength in the following tables. Separately, a tire was produced usingan RFL formulation which was ordinarily used as a tire cord adhesive andrun in the same manner as in the tire of Example 37. The cord tenacityand the adhesion strength of the tire after running are also shown inthe folloiwng tables as the reference. Running Cord tenacity Adhesionstrength distance after running after running (km) (N) (N/cord)Comparative Example 14 10 228 3 (control tire) Example 37 10,010 242 21(inventive tire) RFL composition 10,010 239 20 (reference)

[0093] TABLE 1-1 Com. Ex. 1 Ex. 1 Ex. 2 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² RIACRYL 3100*³ BAC45*⁴ 12 5012 50 12 50 Component D Monofunctional compound SR-285*⁸ 10 10 10SR-440*⁹ 15 AMP-60G*¹⁰ Styrene 5 5 5 Polyfunctional compound 9PG*¹¹ 1513 13 APG-400*¹² 15 15 15 Component E SR-348*¹³ 30 30 30 KAYARAD R551*¹⁴5 BEAMSET 750*¹⁵ KAYARAD R-712*¹⁶ Component B Amine compoundDibutylamine Ethylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ AnilinePyridine 20 15 Tetramethylthiourea Polymerizable monomer 4-vinylpyridineAcrylamide N-vinyl pyrrolidone Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARAD THE-330*¹⁷KAYARAD TPA-320*¹⁸ KAYARAD TPA-330*¹⁹ 20 10 20 10 20 10 BEAMSET 710*²⁰BEAMSET 700*²¹ Epoxy compound ENA*⁶ High-molecular filler HYCARATBN*⁵1300 × 16 ISOBAN 10*⁷ 5 5 5 2 5 2 VIRON 300*²⁷ Inorganic filler NANOMERPGW*²² 2 2 2 Photoinitiator KAYACURE DETX-S*²³ 3 3 3 3 3 3 KAYACUREDMBI*²⁴ Adherend Polyester film Polyester film Polyester film Radiationconditions UV exposure (mJ/cm²) 500 500 500 500 500 500 UV exposure time(s) 5 5 5 5 5 5 EB exposure (MRad) 0 0 0 0 0 0 Results of film peel testPeel strength (N/25 mm) 8 249 231 Rubber adhesion E A+ A Results of cordtensile test Cord tension (N/cord) — — — Rubber adhesion — — — Resultsof differential scanning calorimetry Heat-of-reaction peak None — —temp. (° C.) Analysis by scanning electron microscope- X-ray analyzerSulfur content in Lower than rubber — — adhesive composition layer

[0094] TABLE 1-2 Ex. 3 Ex. 1 Com. Ex. 2 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) RIACRYL 3100^(*3) 5BAC45^(*4) 12 45 12 50 Component D Monofunctional compound SR-285^(*8)10 10 SR-440^(*9) AMP-60G^(*10) 13 9 54 Styrene 5 5 6 Polyfunctionalcompound 9PG^(*11) APG-400^(*12) 15 15 13 9 18 Component E SR-348^(*13)30 30 KAYARAD R551^(*14) BEAMSET 750^(*15) KAYARAD R-712^(*16) 10 10 15Component B Amine compound Dibutylamine Ethylenediamine TOMIDE 252^(*25)FUJICURE 5100^(*26) Aniline Pyridine 15 10 TetramethylthioureaPolymerizable monomer 4-vinylpyridine 15 Acrylamide N-vinyl pyrrolidoneVulcanization accelerator Diphenylguanidine 2-methylimidazole ComponentC or F KAYARAD THE-330^(*17) 20 7 KAYARAD TPA-320^(*18) KAYARADTPA-330^(*19) 20 10 20 10 BEAMSET 710^(*20) BEAMSET 700^(*21) Epoxycompound ENA^(*6) 20 High-molecular filler HYCAR ATBN^(*5) 1300 × 16 6ISOBAN 10^(*7) 5 2 5 2 5 VIRON 300^(*27) 2 3 Inorganic filler NANOMERPGW^(*22) 2 2 Photoinitiator KAYACURE DETX-S^(*27) 3 3 3 3 3 3 KAYACUREDMBI^(*24) Adherend Polyester film Polyester film Polyester filmRadiation conditions UV exposure (mJ/cm²) 500 500 500 500 500 500 UVexposure time (s) 5 5 5 5 5 5 EB exposure (MRad) 0 0 0 0 0 0 Results offilm peel test Peel strength (N/25 mm) 220 224 20 Rubber adhesion A A EResults of cord tensile test Cord tension (N/cord) — — — Rubber adhesion— — — Results of differential scanning calorimetry Heat-of-reaction peak— — None temp. (° C.) Analysis by scanning electron microscope-X-rayanalyzer Sulfur content in adhesive — — Lower than rubber compositionlayer layer

[0095] TABLE 1-3 Ex. 5 Ex. 6 Ex. 7 Undercoat Adhesive Undercoat AdhesiveUndercoat Adhesive layer layer layer layer layer layer Component ARIACRYL 3801^(*1) RIACRYL 3500^(*2) RIACRYL 3100^(*3) 5 10 5 19 5 34BAC45^(*4) Component D Monofunctional compound SR-285^(*8) 5 SR-440^(*9)AMP-60G^(*10) 9 25 9 3 9 3 Styrene 6 3 6 6 6 5 Polyfunctional compound9PG^(*11) APG-400^(*12) 9 18 9 18 9 18 Component E SR-348^(*13) KAYARADR551^(*14) BEAMSET 750^(*15) KAYARAD R-712^(*16) 15 15 4 15 Component BAmine compound Dibutylamine Ethylenediamine TOMIDE 252^(*25) FUJICURE5100^(*26) Aniline Pyridine 2 2 6 Tetramethylthiourea Polymerizablemonomer 4-vinylpyridine 25 20 18 Acrylamide N-vinylpyrrolidoneVulcanization accelerator Diphenylguanidine 2-methylimidazole ComponentC or F KAYARAD THE-330^(*17) 20 7 20 15 20 9 KAYARAD TPA-320^(*18)KAYARAD TPA-330^(*19) BEAMSET 710^(*20) BEAMSET 700^(*21) Epoxy compoundENA^(*6) 20 5 20 5 20 2 High-molecular filler HYCAR ATBN^(*5) 1300 × 166 6 6 ISOBAN 10^(*7) 5 5 5 VIRON 300^(*27) 2 2 2 Inorganic fillerNANOMER PGW^(*22) 2 2 Photoinitiator KAYACURE DETX-S^(*23) 3 3 3 3 3 3KAYACURE DMBI^(*24) Adherend Polyester film Polyester film Polyesterfilm Radiation conditions UV exposure (mJ/cm²) 500 500 500 500 500 500UV exposure time (s) 5 5 5 5 5 5 EB exposure (MRad) 0 0 0 0 0 0 Resultsof film peel test Peel strength (N/25 mm) 63 72 206 Rubber adhesion D DB Results of cord tensile test Cord tension (N/cord) — — — Rubberadhesion — — — Results of differential scanning calorimetryHeat-of-reaction peak — 160° C. — temp. (° C.) Analysis by scanningelectron microscope-X-ray analyzer Sulfur content in adhesive — Lowerthan rubber — composition layer layer

[0096] TABLE 1-4 Ex. 8 Ex. 9 Ex. 10 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) RIACRYL 3100^(*3) 5 45 555 5 67 BAC45^(*4) Component D Monofunctional compound SR-285^(*8)SR-440^(*9) AMP-60G^(*10) 9 9 9 Styrene 6 3 6 6 Polyfunctional compound9PG^(*11) APG-400^(*12) 9 18 9 18 9 12 Component E SR-348^(*13) KAYARADR551^(*14) BEAMSET 750^(*15) KAYARAD R-712^(*16) 15 3 15 15 Component BAmine compound Dibutylamine Ethylenediamine TOMIDE 252^(*25) FUJICURE5100^(*26) Aniline Pyridine Tetramethylthiourea Polymerizable monomer4-vinylpyridine 15 15 15 Acrylamide N-vinylpyrrolidone 4 Vulcanizationaccelerator Diphenylguanidine 2-methylimidazole Component C or F KAYARADTHE-330^(*17) 20 7 20 7 20 4 KAYARAD TPA-320^(*18) KAYARAD TPA-330^(*19)BEAMSET 710^(*20) BEAMSET 700^(*21) Epoxy compound ENA^(*6) 20 20 20High-molecular filler HYCAR ATBN^(*5) 1300 × 16 6 6 6 ISOBAN 10^(*7) 5 55 VIRON 300^(*27) 2 2 2 2 2 Inorganic filler NANOMER PGW^(*22)Photoinitiator KAYACURE DETX-S^(*23) 3 3 3 3 3 2 KAYACURE DMBI^(*24)Adherend Polyester film Polyester film Polyester film Radiationconditions UV exposure (mJ/cm²) 500 500 500 500 500 500 UV exposure time(s) 5 5 5 5 5 5 EB exposure (M Rad) 0 0 0 0 0 0 Results of film peeltest Peel strength (N/25 mm) 257 260 186 Rubber adhesion A+ A+ B Resultsof cord tensile test Cord tension (N/cord) — — — Rubber adhesion — — —Results of differential scanning calorimetry Heat-of-reaction peak 150°C. — — temp. (° C.) Analysis by scanning electron microscope-X-rayanalyzer Sulfur contant in adhesive Higher than — — composition layerrubber layer

[0097] TABLE 1-5 Ex. 11 Com. Ex. 3 Ex. 12 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² 10 57 RIACRYL 3100*³ 5 81 5100 BAC45*⁴ Component D Monofunctional compound SR-285*⁸ SR-440*⁹AMP-60G*¹⁰ 9 9 12 Styrene 6 6 6 Polyfunctional compound 9PG*¹¹APG-400*¹² 9 5 9 0 12 18 Component E SR-348*¹³ KAYARAD R551*¹⁴ BEAMSET750*¹⁵ 10 KAYARAD R-712*¹⁶ 15 15 20 Component (B) Amine compoundDibutylamine Ethylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ AnilinePyridine Tetramethylthiourea Polymerizable monomer 4-vinylpyridine 9 15Acrylamide N-vinylpyrrolidone Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARAD THE-330*¹⁷20 3 20 0 KAYARAD TPA-320*¹⁸ KAYARAD TPA-330*¹⁹ 24 7 BEAMSET 710*²⁰BEAMSET 700*²¹ Epoxy compound ENA*⁶ 20 20 High-molecular fillerHYCARATBN*⁵ 1300 × 16 6 6 ISOBAN 10*⁷ 5 5 VIRON 300*²⁷ 2 2 Inorganicfiller NANOMER PGW*²² 3 Photoinitiator KAYACURE DETX-S*²⁷ 3 2 3 0 3 3KAYACURE DMBI*²⁴ Adherend Polyester film Polyester film Polyester filmRadiation conditions UV exposure (mJ/cm²) 1000 1000 1000 1000 1000 500UV exposure time (sec) 10 10 10 10 10 5 EB exposure (MRad) 0 0 0 0 0 0Results of film peel test Peel strength (N/25 mm) 98 8 270 Rubberadhesion C E A Results of cord tensile test Cord tension (N/cord) — — —Rubber adhesion Results of differential scanning calorimetryHeat-of-reaction peak — None — temp. (° C.) Analysis by scanningelectron microscope-X-ray analyzer Sulfur content in adhesive- Lowerthan rubber- composition layer layer

[0098] TABLE 1-6 Com. Ex. 4 Ex. 13 Com. Ex. 5 Undercoat AdhesiveUndercoat Adhesive Undercoat Adhesive layer layer layer layer layerlayer Component A RIAGRYL 3801^(*1) 10 50 10 50 5 42 RIACRYL 3500^(*2)RIACRYL 3100^(*3) BAC45^(*4) Component D Monofunctional compoundSR-285^(*8) 2 15 2 SR-440^(*9) 10 15 AMP-60G^(*10) StyronePolyfunctional compound 9PG^(*11) APG-400^(*12) 20 17 8 20 Component ESR-348^(*13) KAYARAD R551^(*14) 32 BEAMSET 750^(*15) 35 35 KAYARADR-712^(*16) Component B Amine compound Dibutylamine EthylenediamineTOMIDE 252^(*25) FUJICURE 5100^(*26) Aniline PyridineTetramethylthiourea Polymerizable monomer 4-vinylpyridine 8 8 AcrylamideN-vinylpyrrohidone 18 Vulcanization accelerator Diphenylguanidine2-methylimidazole Component C or F KAYARAD THE-330^(*17) KAYARADTPA-320^(*18) KAYARAD TPA-330^(*19) BEAMSET 710^(*20) 20 12 20 12BEAMSET 700^(*21) 25 18 Epoxy compound ENA^(*6) 10 10 10 High-molecularfiller HYCAR ATBN^(*5) 1300 × 16 5 ISOBAN 10^(*7) 12 12 VIRON 300^(*27)Inorganic filler NANOMER PGW^(*22) 3 3 Photoinitiator KAYACUREDETX-S^(*23) KAYACURE DMBI^(*24) 3 3 3 3 2 2 Adherend Polyester filmPolyester film Polyester film Radiation conditions UV exposure (mJ/cm²)500 500 500 500 1000 1000 UV exposure time (s) 5 5 5 5 10 10 EB exposure(MRad) 0 0 0 0 0 0 Results of film peel test Peel strength (N/25 mm) 6254 13 Rubber adhesion E A+ E Results of cord tensile test Cord tension(N/cord) — — — Rubber adhesion — — — Results of differential scanningcalorimetry Heat-of-reaction peak — — — tomp. (° C.) Analysis byscanning electron microscope-X-ray analyzer Sulfur content in adhesive —— — composition layer

[0099] TABLE 1-7 Ex. 14 Com. Ex. 6 Ex. 15 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) 5 42 RIACRYL 3500^(*2) 10 60 10 42 RIACRYL3100^(*3) BAC45^(*4) Component D Monofunctional compound SR-285^(*8)SR-440^(*9) 10 5 10 AMP-60G^(*10) Styrene 10 3 Polyfunctional compound9PG^(*11) 14 14 APG-400^(*12) 8 15 15 20 Component E SR-348^(*13)KAYARAD R551^(*14) 32 18 BEAMSET 750^(*15) KAYARAD R-712^(*18) 36 18Component B Amine compound Dibutylamine 4 23 Ethylenediamine 15 TOMIDE252^(*25) FUJICURE 5100^(*26) Aniline Pyridine TetramethylthioureaPolymerizable monomer 4-vinylpyridine 4 Acrylamide N-vinylpyrrolidoneVulcanization accelerator Diphenylguanidine 2-methylimidazole ComponentC or F KAYARAD THE-330^(*17) 8 8 KAYARAD TPA-320^(*18) 12 12 KAYARADTPA-330^(*19) 6 6 5 BEAMSET 710^(*20) BEAMSET 700^(*21) 25 18 Epoxycompound ENA^(*6) 10 6 6 High-molecular filler HYCAR ATBN^(*5) 1300 × 165 10 ISOBAN 10^(*7) VIRON 300^(*27) Inorganic filler NANOMER PGW^(*22) 33 2 Photoinitiator KAYACURE DETX-S^(*23) 2 2 2 2 KAYACURE DMBI^(*24) 2 2Adherend Polyester film Polyester film Polyester film Radiationconditions UV exposure (mJ/cm²) 1000 1000 1000 500 1000 500 UV exposuretime (s) 10 10 10 5 10 5 EB exposure (MRad) 0 0 0 0 0 0 Results of filmpeel test Peel strength (N/25 mm) 190 22 178 Rubber adhesion B E BResults of cord tensile test Cord tension (N/cord) — — — Rubber adhesion— — — Results of differential scanning calorimetry Heat-of-reaction peak156° C. — 159° C. temp. (° C.) Analysis by scanning electronmicroscope-X-ray analyzer Sulfur content in adhesive Higher than —Higher than composition rubber layer — rubber layer

[0100] TABLE 1-8 Ex. 16 Ex. 17 Ex. 18 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² 10 45 10 45 10 45 RIACRYL3100*³ BAC45*^(d) Component D Monofunctional compound SR-285*⁸ SR-440*⁹10 3 10 3 AMP-60G*¹⁰ Styrene 10 3 Polyfunctional compound 9PG*¹¹ 14 1414 APG-400*¹² 15 15 15 Component E SR-348*¹³ KAYARAD R551*¹⁴ 18 18 18BEAMSET 750*¹⁵ KAYARAD R-712*¹⁶ 18 18 18 Component B Amine compoundDibutylamino Ethylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ 4 Aniline 1520 Pyridine Tetramethylthiourea Polymerizable monomer 4-vinylpyridine 4Acrylamide N-vinylpyrrolidone 4 Vulcanization acceleratorDiphenylguanidine 15 2-methylimidazole Component C or F KAYARADTHE-330*¹⁷ 8 8 8 KAYARAD TPA-320*¹⁸ 12 12 12 KAYARAD TPA-330*¹⁹ 6 6 6BEAMSET 710*²⁰ BEAMSET 700*²¹ Epoxy compound ENA*⁶ 6 6 6 High-molecularfiller HYCARATBN*⁵ 1300 × 16 10 5 10 ISOBAN 10*⁷ VIRON 300*²⁷ Inorganicfiller NANOMER PGW*²² 2 2 2 Photoinitiator KAYACURE DETX-S*²³ 2 2 2 2 22 KAYACURE DMBI*²¹ Adherend Polyester film Polyester film Polyester filmRadiation conditions UV exposure (mJ/cm²) 1000 500 1000 500 1000 500 UVexposure time (s) 10 5 10 5 10 5 EB exposure (MRad) 0 0 0 0 0 0 Resultsof film peel test Peel strength (N//25 mm) 159 204 188 Rubber adhesion CB B Results of cord tensile test Cord tension (N/cord) — — — Rubberadhesion — — — Results of differential scanning calorimetryHeat-of-reaction peak — — — temp. (° C.) Analysis by scanning electronmicroscope-X-ray analyzer Sulfur content in adhesive Higher than Higherthan — composition layer rubber layer rubber layer

[0101] TABLE 1-9 Ex. 19 Ex. 20 Ex. 21 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) 10 45 10 45 10 45RIACRYL 3100^(*3) BAC45^(*4) Component D Monofunctional compoundSR-285^(*8) SR-440^(*9) 10 3 10 3 10 3 AMP-60G^(*10) StyrenePolyfunctional compound 9PG^(*11) 14 14 14 APG-400^(*12) 15 15 15Component E SR-348^(*13) KAYARAD R551^(*14) 18 18 18 BEAMSET 750^(*15)KAYARAD R-712^(*16) 18 18 18 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252^(*25) FUJICURE 5100^(*26) Aniline PyridineTetramethylthiourea 15 Polymerizable monomer 4-vinylpyridine Acrylamide4 15 N-vinylpyrrolidone Vulcanization accelerator Diphenylguanidine 42-methylimidazole 4 15 Component C or F KAYARAD THE-330^(*17) 8 8 8KAYARAD TPA-320^(*18) 12 12 12 KAYARAD TPA-330^(*19) 6 6 6 BEAMSET710^(*20) BEAMSET 700^(*21) Epoxy compound ENA^(*6) 6 6 6 High-molecularfiller HYCAR ATBN^(*5) 1300 × 16 10 10 10 ISOBAN 10^(*7) VIRON 300^(*27)Inorganic filler NANOMER PGW^(*22) 2 2 2 Photoinitiator KAYACUREDETX-S^(*28) 2 2 2 2 2 2 KAYACURE DMBI^(*24) Adherend Polyester filmPolyester film Polyester film Radiation conditions UV exposure (mJ/cm²)1000 500 1000 500 1000 500 UV exposure time (s) 10 5 10 5 10 5 EBexposure (MRad) 0 0 0 0 0 0 Results of film peel test Peel strength(N/25 mm) 147 152 227 Rubber adhesion C C A Results of cord tensile testCord tension (N/cord) — — — Rubber adhesion — — — Results ofdifferential scanning calorimetry Heat-of-reaction peak — — — temp. (°C.) Analysis by scanning electron microscope-X-ray analyzer Sulfurcontent in adhesive Higher than Higher than Higher than compositionlayer rubber layer rubber layer rubber layer

[0102] TABLE 1-10 Ex. 22 Com. Ex. 7 Ex. 23 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) 10 45 10 54 10 54RIACRYL 3100^(*3) BAC45^(*4) Component D Monofunctional compoundSR-285^(*8) SR-440^(*8) 10 3 10 10 AMP-60G^(*10) Styrone 23Polyfunctional compound 9PG^(*11) 14 APG-400^(*12) 15 14 14 14 14Component E SR-348^(*13) KAYARAD R551^(*14) 18 18 18 BEAMSET 750^(*15)KAYARAD R-712^(*16) 18 18 18 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252^(*25) FUJICURE 5100^(*26) Aniline PyridineTetramethylthiourea Polymerizable monomer 4-vinylpyridine 23 AcrylamideN-vinylpyrrolidone 4 15 4 4 Vulcanization accelerator Diphenylguanidine2-methylimidazole Component C or F KAYARAD THE-330^(*17) 8 KAYARADTPA-320^(*18) 12 12 6 12 6 KAYARAD TPA-330^(*19) 6 6 6 BEAMSET 710^(*20)BEAMSET 700^(*21) Epoxy compound ENA^(*6) 6 6 6 High-molecular fillerHYCAR ATBN^(*5) 1300 × 16 10 ISOBAN 10^(*7) VIRON 300^(*27) Inorganicfiller NANOMER PGW^(*22) 2 Photoinitiator KAYACURE DETX-S^(*23) 2 2 2 32 3 KAYACURE DMBI^(*24) Adherend Polyester film Polyester film Polyesterfilm Radiation conditions UV exposure (mJ/cm²) 1000 500 1000 500 1000500 UV exposure time (sec) 10 5 10 5 10 5 EB exposure (MRad) 0 0 0 0 0 0Results of film peel test Peel strength (N/25 mm) 208 15 229 Rubberadhesion A E A Results of cord tensile test Cord tension (N/cord) — — —Rubber adhesion — — — Results of differential scanning calorimetryHeat-of-reaction peak — — — temp. (° C.) Analysis by scanning electronmicroscope-X-ray analyzer Sulfur content in adhesive — — — compositionlayer

[0103] TABLE 1-11 Com. Ex. 8 Ex. 24 Ex. 25 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) 10 53 10 53 10 53RIACRYL 3100^(*3) BAC45^(*4) Component D Monofunctional compoundSR-285^(*8) 5 4 3 SR-440^(*9) 10 10 10 5 AMP-60G^(*10) Styrene 14 8 6Polyfunctional compound 9PG^(*11) APG-400^(*12) 14 14 14 14 14 14Component E SR-348^(*13) KAYARAD R551^(*14) 18 18 18 BEAMSET 750^(*15)KAYARAD R-712^(*16) 18 18 18 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252^(*25) FUJICURE 5100^(*26) Aniline PyridineTetramethylthiourea Polymerizable monomer 4-vinylpyridine 6 10Acrylamide N-vinylpyrrolidone 4 4 4 Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARADTHE-330^(*17) KAYARAD TPA-320^(*18) 12 6 12 6 12 6 KAYARAD TPA-330^(*19)6 6 6 BEAMSET 710^(*20) BEAMSET 700^(*21) Epoxy compound ENA^(*6) 6 5 66 6 High-molecular filler HYCAR ATBN^(*6) 1300 × 16 ISOBAN 10^(*7) VIRON300^(*27) Inorganic filler NANOMER PGW^(*22) Photonitiator KAYACUREDETX-S^(*23) 2 3 2 3 2 3 KAYACURE DMBI^(*24) Adherend Polyester filmPolyester film Polyester film Radiation conditions UV exposure (mJ/cm²)1000 500 1000 500 1000 500 UV exposure time (s) 10 5 10 5 10 5 EBexposure (MRad) 0 0 0 0 0 0 Results of film peel test Peel strength(N/25 mm) 14 100 259 Rubber adhesion E C A+ Results of cord tensile testCord tension (N/cord) — — — Rubber adhesion — — — Results ordifferential scanning calorimetry Heat-of-reaction peak — 167 160 temp.(° C.) Analysis by scanning electron microscope-X-ray analyzer Sulfurcontent in adhesive — Higher than Higher than composition layer rubberlayer rubber layer

[0104] TABLE 1-12 Ex. 26 Ex. 27 Ex. 28 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) 10 53 10 38 10 29RIACRYL 3100^(*3) BAC45^(*4) Component D Monofunctional compoundSR-285^(*8) SR-440^(*9) 10 10 10 AMP-60G^(*10) 4 Styrene 3Polyfunctional compound 9PG^(*11) APG-400^(*12) 14 14 14 14 14 10Component E SR-348^(*13) KAYARAD R551^(*14) 18 18 18 BEAMSET 750^(*15)KAYARAD R-712^(*16) 18 18 18 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252^(*25) FUJICURE 5100^(*26) Aniline PyridineTetramethylthiourea Polymerizable monomer 4-vinylpyridine 14 39 53Acrylamide N-vinylpyrrolidone 4 4 4 Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARADTHE-330^(*17) KAYARAD TPA-320^(*18) 12 6 12 6 12 5 KAYARAD TPA-330^(*19)6 6 6 BEAMSET 710^(*20) BEAMSET 700^(*21) Epoxy compound ENA^(*6) 6 3 66 High-molecular filler HYCAR ATBN^(*5) 1300 × 16 ISOBAN 10^(*7) VIRON300^(*27) Inorganic filler NANOMER PGW^(*22) Photopolymerizationinitiator KAYACURE DETX-S^(*23) 2 3 2 3 2 3 KAYACURE DMBI^(*24) AdherendPolyester film Polyester film Polyester film Radiation conditions UVexposure (mJ/cm²) 1000 500 1000 500 1000 500 UV exposure time (s) 10 510 5 10 5 EB exposure (MRad) 0 0 0 0 0 0 Results of film peel test Peelstrength (N/25 mm) 245 233 162 Rubber adhesion A A B Results of cordtensile test Cord tension (N/cord) — — — Rubber adhesion — — — Resultsof differential scanning calorimetry Heat-of-reaction peak — 144 — temp.(° C.) Analysis by scanning electron microscope-X-ray analyzer Sulfurcontent in adhesive — Higher than — composition layer rubber layer

[0105] TABLE 1-13 Com. Ex. 9 Ex. 29 Ex. 30 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801^(*1) RIACRYL 3500^(*2) 10 10 44 10 44 RIACRYL3100^(*3) BAC45^(*4) Component D Monofunctional compound SR-285^(*8)SR-440^(*9) 10 10 10 AMP-60G^(*10) Styrene Polyfunctional compound9PG^(*11) APG-400^(*12) 14 14 14 14 14 Component E SR-348^(*13) KAYARADR551^(*14) 18 18 18 BEAMSET 750^(*15) KAYARAD R-712^(*16) 18 18 18Component B Amine compound Dibutylamine Ethylenediamine TOMIDE 252^(*25)FUJICURE 5100^(*26) Aniline Pyridine 10 10 TetramethylthioureaPolymerizable monomer 4-vinylpyridine 100 23 23 AcrylamideN-vinylpyrrolidone 4 4 4 Vulcanization accelerator Diphenylguanidine2-methylimidazole Component C or F KAYARAD THE-330^(*17) KAYARADTPA-320^(*18) 12 12 6 12 6 KAYARAD TPA-330^(*19) 6 6 6 BEAMSET 710^(*20)BEAMSET 700^(*21) Epoxy compound ENA^(*6) 6 6 6 High-molecular fillerHYCAR ATBN^(*5) 1300 × 16 ISOBAN 10^(*7) VIRON 300^(*27) Inorganicfiller NANOMER PGW^(*22) Photoinitiator KAYACURE DETX-S^(*23) 2 2 3 2 3KAYACURE DMBI^(*24) Adherend Polyester film Polyester film Polyesterfilm Radiation conditions UV exposure (mJ/cm²) 1000 500 0 0 0 0 UVexposure time (s) 10 5 0 0 0 0 EB exposure (MRad) 0 0 40 20 40 15Results of film peel test Peel strength (N/25 mm) 13 231 224 Rubberadhesion E A A Results of cord tensile test Cord tension (N/cord) — — —Rubber adhesion — — — Results of differential scanning calorimetryHeat-of-reaction peak — — — temp. (° C.) Analysis by scanning electronmicroscope-X-ray analyzer Sulfur content in adhesive — — — compositionlayer

[0106] TABLE 1-14 Ex. 31 EX. 32 Ex. 33 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² 10 47 10 47 10 47 RIACRYL3100*³ BAC45*⁴ Component D Monofunctional compound SR-285*⁸ SR-440*⁹ 1010 10 AMP-60G*¹⁰ Styrene Polyfunctional compound 9PG*¹¹ APG-400*¹² 14 1414 14 14 14 Component E SR-348*¹³ KAYARAD R551*¹⁴ 18 18 18 BEAMSET750*¹⁵ KAYARAD R-712*¹⁶ 18 18 18 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ Aniline Pyridine 10 10 10Tetramethylthiourea Polymerizable monomer 4-vinylpyridine 23 23 23Acrylamide N-vinylpyrrolidone 4 4 4 Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARAD THE-330*¹⁷KAYARAD TPA-320*¹⁸ 12 6 12 6 12 6 KAYARAD TPA-330*¹⁹ 6 6 6 BEAMSET710*²⁰ BEAMSET 700*²¹ Epoxy compound ENA*⁶ 8 8 8 High-molecular fillerHYCARATBN*⁵ 1300 × 16 ISOBAN 10*⁷ VIRON 300*²⁷ Inorganic filler NANOMERPGW*²² Photoinitiator KAYACURE DETX-S*²⁷ KAYACURE DMBI*²⁴ AdherendPolyester film Polyester film Polyester film Radiation conditions UVexposure (mJ/cm²) 1000 0 1000 0 0 0 UV exposure time (s) 10 0 10 0 0 0EB exposure (MRad) 0 15 0 7 25 7 Results of film peel test Peel strength(N/25 mm) 239 215 244 Rubber adhesion A A A Results of cord tensile testCord tension (N/cord) — — — Rubber adhesion — — — Results ofdifferential scanning calorimetry Heat-of-reaction peak — — — temp. (°C.) Analysis by scanning electron microscope-X-ray analyzer Sulfurcontent in adhesive — — — composition

[0107] Com. Ex. 10 Com. Ex. 11 Ex. 34 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² 10 10 47 RIACRYL 3100*³ 10 54BAC45*⁴ Component D Monofunctional compound SR-285*⁸ SR-440*⁹ 10 44 1030 10 AMP-60G*¹⁰ Styrene Polyfunctional compound 9PG*¹¹ APG-400*¹² 14 1414 14 14 14 Component E SR-348*¹³ KAYARAD R551*¹⁴ 18 18 18 BEAMSET750*¹⁵ KAYARAD R-712*¹⁶ 18 18 18 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ Aniline Pyridine 10Tetramethylthiourea Polymerizable monomer 4-vinylpyridine 23 23Acrylamide N-vinylpyrrolidone 4 4 4 Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARAD THE-330*¹⁷KAYARAD TPA-320*¹⁸ 12 6 12 6 12 6 KAYARAD TPA-330*¹⁹ 6 6 6 BEAMSET710*²⁰ BEAMSET 700*²¹ Epoxy compound ENA*⁶ 6 6 8 High-molecular fillerHYCAR ATBN*⁵ 1300 × 16 ISOBAN 10*⁷ VIRON 300*²⁷ Inorganic filler NANOMERPGW*²² Photoinitiator KAYACURE DETX-S*²³ 2 3 2 3 0 3 KAYACURE DMBI*²⁴Adherend Polyester film Polyester film Polyester film Radiationconditions UV exposure (mJ/cm²) 0 0 0 0 0 0 UV exposure time (s) 0 0 0 00 0 EB exposure (MRad) 40 7 40 7 20 0 Results of film peel test Peelstrength (N/25 mm) 9 13  86 Rubber adhesion E E D Results of cordtensile test Cord tension (N/cord) — — — Rubber adhesion — — — Resultsof differential scanning calorimetry Heat-of-reaction peak — — 142 temp.(° C.) Analysis by scanning electron microscope-X-ray analyzer Sulfurcontent in adhesive — — Higher than composition layer rubber layer

[0108] TABLE 1-16 Ex. 35 Ex. 36 Com. Ex. 12 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² RIACRYL 3100*³ 10 54 10 54 10BAC45*⁴ Component D Monofunctional compound SR-285*⁸ SR-440*⁹ 10 10 1054 AMP-60G*¹⁰ Styrene Polyfunctional compound 9PG*¹¹ APG-400*¹² 14 14 1414 14 14 Component E SR-348*¹³ KAYARAD R551*¹⁴ 18 18 18 BEAMSET 750*¹⁵KAYARAD R-712*¹⁶ 18 18 18 Component B Amine compound Dibutylamine 10Ethylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ Aniline PyridineTetramethylthiourea Polymerizable monomer 4-vinylpyridine 13 23Acrylamide N-vinylpyrrolidone 4 4 4 Vulcanization acceleratorDiphenylguanidine 2-methylimidazole 23 Component C or F KAYARADTHE-330*¹⁷ KAYARAD TPA-320*¹⁸ 12 6 12 6 12 6 KAYARAD TPA-330*¹⁹ 6 6 6BEAMSET 710*²⁰ BEAMSET 700*²¹ Epoxy compound ENA*⁶ 6 6 6 High-molecularfiller HYCAR ATBN*⁵ 1300 × 16 ISOBAN 10*⁷ VIRON 300*²⁷ Inorganic fillerNANOMER PGW*²² Photoinitiator KAYACURE DETX-S*²³ 2 3 2 3 2 3 KAYACUREDMBI*²⁴ Adherend Polyester film Polyester film Polyester film Radiationconditions UV exposure (mJ/cm²) 1000 0 1000 0 1000 0 UV exposure time(s) 10 0 10 0 10 0 EB exposure (MRud) 0 0 0 0 40 0 Results of film peeltest Peel strength (N/25 mm) 189 175 16 Rubber adhesion B B E Results ofcord tensile test Cord tension (N/cord) — — — Rubber adhesion — — —Results of differential scanning calorimetry Heat-of-reaction peak — — —temp. (° C.) Analysis by scanning electron microscope-X-ray analyzerSulfur content in adhesive — — — composition layer

[0109] TABLE 1-17 Com. Ex. 13 Com. Ex. 14 Ex. 37 Undercoat AdhesiveUndercoat Adhesive Undercoat Adhesive layer layer layer layer layerlayer Component A RIACRYL 3801*¹ RIACRYL 3500*² RIACRYL 3100*³ 10 54 555 5 55 BAC45*⁴ Component D Monofunctional compound SR-285*⁸ SR-440*⁹ 1023 AMP-60G*¹⁰ 9 9 Styrene 17 Polyfunctional compound 9PG*¹¹ APG-400*¹²14 14 9 18 9 18 Component E SR-348*¹³ KAYARAD R551*¹⁴ 18 BEAMSET 750*¹⁵KAYARAD R-712*¹⁶ 18 20 20 Component B Amine compound DibutylamineEthylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ Aniline PyridineTetramethylthiourea Polymerizable monomer 4-vinylpyridine 17 Acrylamide6 6 N-vinylpyrrolidone 4 Vulcanization accelerator Diphenylguanidine2-methylimidazole Component C or F KAYARAD THE-330*¹⁷ 15 7 15 7 KAYARADTPA-320*¹⁸ 12 6 KAYARAD TPA-330*¹⁹ 6 BEAMSET 710*²⁰ BEAMSET 700*²¹ Epoxycompound ENA*⁶ 6 20 20 High-molecular filler HYCAR ATBN*⁵ 1300 × 16 6 6ISOBAN 10*⁷ 7 7 VIRON 300*²⁷ Inorganic filler NANOMER PGW*²²Photoinitiator KAYACURE DETX-S*²³ 2 3 3 3 3 3 KAYACURE DMBI*²⁴ AdherendPolyester film Polyester cord Polyester cord Radiation conditions UVexposure (mJ/cm²) 1000 0 1000 1000 1000 1000 UV exposure time (s) 10 010 10 10 10 EB exposure (MRad) 40 0 0 0 0 0 Results of film peel testPeel strength (N/25 mm) 11 — — Rubber adhesion E — — Results of cordtensile test Cord tension (N/cord) — 4 22 Rubber adhesion — E A Resultsof differential scanning calorimetry Heat-of-reaction peak — — — temp.(° C.) Analysis by scanning electron microscope-X-ray analyzer Sulfurcontent in adhesive — — — composition layer

[0110] TABLE 1-18 Ex. 38 Ex. 39 Ex. 40 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ 6 50 RIACRYL 3500*² 6 50 RIACRYL 3100*³ 6 56BAC45*⁴ Component D Monofunctional compound SR-285*⁸ 8 10 SR-440*⁹ 10 8AMP-60G*¹⁰ 5 15 10 Styrene 6 Polyfunctional compound 9PG*¹¹ 12 14APG-400*¹² 20 10 10 20 Component E SR-348*¹³ 32 KAYARAD R551*¹⁴ 20BEAMSET 750*¹⁵ KAYARAD R-712*¹⁶ 30 Component B Amine compoundDibutylamine Ethylenediamine TOMIDE 252*²⁵ FUJICURE 5100*²⁶ 10 AnilinePyridine 5 15 Tetramethylthiourea Polymerizable monomer 4-vinylpyridineAcrylamide N-vinylpyrrolidone 9 10 Vulcanization acceleratorDiphenylguanidine 2-methylimidazole Component C or F KAYARAD THE-330*¹⁷8 KAYARAD TPA-320*¹⁸ KAYARAD TPA-330*¹⁹ 20 7 BEAMSET 710*²⁰ 15 BEAMSET700*²¹ 10 8 Epoxy compound ENA*⁸ 20 High-molecular filler HYCAR ATBN*⁵1300 × 16 ISOBAN 10*⁷ 5 VIRON 300*²⁷ 14 10 Inorganic filler NANOMERPGW*²² 2 2 Photoinitiator KAYACURE DETX-S*²³ 3 3 2 2 KAYACURE DMBI*²⁴ 33 Adherend Polyester cord Polyester cord Polyester cord Radiationconditions UV exposure (mJ/cm²) 1000 1000 1000 1000 1000 1000 UVexposure time (s) 10 10 10 10 10 10 EB exposure (MRad) 0 0 0 0 0 0Results of film peel test Peel strength (N/25 mm) — — — Rubber adhesion— — — Results of cord tensile test Cord tension (N per cord) 15 20 19Rubber adhesion B A B Results of differential scanning calorimetryHeat-of-reaction peak — — — temp. (° C.) Analysis by scanning electronmicroscope-X-ray analyzer Sulfur content in adhesive — — — compositionlayer

[0111] TABLE 1-19 Ex. 41 Ex. 42 Ex. 43 Undercoat Adhesive UndercoatAdhesive Undercoat Adhesive layer layer layer layer layer layerComponent A RIACRYL 3801*¹ RIACRYL 3500*² RIACRYL 3100*³ 6 56 6 56BAC45*⁴ 5 50 Component D Monofunctional compound SR-285*⁸ 10 SR-440*⁹AMP-60G*¹⁰ 15 15 8 15 8 Styrene Polyfunctional compound 9PG*¹¹APG-400*¹³ 10 15 15 10 15 10 Component E SR-348*¹³ 32 KAYARAD R551*¹⁴ 2020 BEAMSET 750*¹⁵ KAYARAD R-712*¹⁶ Component B Amine compoundDibutylamine Ethylenediamine TOMIDE 252*²⁵ 10 10 10 FUJICURE 5100*²⁶Aniline Pyridine 10 Tetramethylthiourea Polymerizable monomer4-vinylpyridine 16 16 Acrylamide N-vinylpyrrolidone Vulcanizationaccelerator Diphenylguanidine 2-methylimidazole Component C or F KAYARADTHE-330*¹⁷ 20 7 KAYARAD TPA-320*¹⁸ KAYARAD TPA-330*¹⁹ BEAMSET 710*²⁰BEAMSET 700*²¹ 12 8 12 8 Epoxy compound ENA*⁶ 10 20 20 High-molecularfiller HYCAR ATBN*⁵ 1300 × 16 ISOBAN 10*⁷ VIRON 300*²⁷ Inorganic fillerNANOMER PGW*²² Photoinitiator KAYACURE DETX-S*²³ 3 3 KAYACURE DMBI*²⁴ 22 2 2 Adherend Polyester cord Polyester cord Nylon cord Radiationconditions UV exposure (mJ/cm²) 1000 1000 1000 1000 0 1000 UV exposuretime (s) 10 10 10 10 0 10 EB exposure (MRad) 0 0 0 0 40 0 Results offilm peel test Peel strength (N/25 mm) — — — Rubber adhesion — — —Results of cord tensile test Cord tension (N/cord) 16 22 24 Rubberadhesion B A A Results of differential scanning calorimetryHeat-of-reaction peak — — — temp. (° C.) Analysis by scanning electronmicroscope-X-ray analyzer Sulfur content in adhesive — — — compositionlayer

INDUSTRIAL APPLICABILITY

[0112] In the process of bonding a rubber to an adherend through theadhesive composition according to the present invention, the adhesivecomposition is irradiated with ultraviolet light or radiation and thenthe vulcanization is preformed while bringing an unvulcanized rubberinto press-contact with the adhesive composition, thereby achieving anexcellent adhesion between the rubber and the adherend. Accordingly, thepresent invention is useful for the production of a rubber-reinforcingmaterial or a rubber article which require a good adhesion between therubber and the adherend.

What is claimed is:
 1. An adhesive composition comprising (A) aconjugated diene polymer having a weight-average molecular weight of 500to 100,000 and (B) an electron pair-donating basic compound.
 2. Theadhesive composition according to claim 1, wherein the electronpair-donating basic compound B is contained in an amount of 0.2 to 50parts by weight based on 100 parts by weight of the conjugated dienepolymer A.
 3. The adhesive composition according to claim 1 or claim 2,wherein a mixture comprising 100 parts by weight of the adhesivecomposition and 3 parts by weight of sulfur shows a heat-of-reactioncurve in which a peak of reaction heat attributable to a vulcanizationreaction is observed in a temperature region of 190° C. or lower whenmeasured at a temperature rise rate of 5° C./min by a differentialscanning calorimeter, said peak being not observed in a heat-of-reactioncurve for a mixture comprising 100 parts by weight of the conjugateddiene polymer A and 3 parts by weight of sulfur as measured under thesame conditions as above.
 4. The adhesive composition according to anyone of claims 1 to 3, wherein when a composite that is prepared bybonding the adhesive composition and a sulfur-containing adherend rubbermixture is measured for a count of fluorescent X-ray from sulfur atom ina cross section parpendicular to a bonding surface by using an electronmicroscope and an X-ray analyzer, a count due to sulfur atom in anadhesive layer is larger than an average distribution of count due tosulfur atom in the adherend rubber.
 5. The adhesive compositionaccording to any one of claims 1 to 4, further comprising (C) a compoundhaving in its molecule three or more functional groups that arecross-linkable by irradiation of ultraviolet light or radiation and/or(D) a compound having in its molecule one or two functional groups thatare radically-polymerizable by irradiation of ultraviolet light orradiation.
 6. The adhesive composition according to any one of claims 1to 5, wherein an end group of the conjugated diene polymer A is selectedfrom the group consisting of vinyl group, acryloyl group, methacryloylgroup, acryloyloxy group, methacryloyloxy group and allyl group.
 7. Theadhesive composition according to any one of claims 1 to 5, wherein anend group of the conjugated diene polymer A is acryloyloxy gpr ormethacryloyloxy group.
 8. The adhesive composition according to any oneof claims 1 to 7, wherein the electron pair-donating basic compound B isa compound containing nitrogen atom having a lone pair or a compoundcapable of forming a compound containing a structure having a lone pairby thermal decomposition.
 9. The adhesive composition according to claim8, wherein the compound containing nitrogen atom having a lone pair isan amine compound or a polymerizable monomer having an aliphatic amineresidue or a heterocyclic amine residue and further having acarbon-carbon double bond.
 10. The adhesive composition according toclaim 9, wherein the amine compound is selected from the groupconsisting of an aliphatic amine, an aromatic amine, an aldehydeamine, aguanidine compound, a thiouric acid compound and a heterocyclic amine.11. The adhesive composition according to claim 10, wherein thealiphatic amine is dibutylamine, ethylenediamine orpolyethylenepolyamine; the aromatic amine is aniline, m-phenylenediamineor 2,4-toluylenediamine, the aldehydeamine is n-butylaldehydeaniline;the guanidine compound is diphenylguanidine or di-o-tolylguanidine; thethiouric acid compound is thiocarbanilide, diethylthiourea ortetramethylthiourea; and the heterocyclic amine is pyridine or2-methylimidazole.
 12. The adhesive composition according to claim 9,wherein the polymerizable monomer is at least one compound selected fromthe group consisting of 2-vinylpyridine, 4-vinylpyridine,m-(N,N-dimethylamino)styrene, p-(N,N-dimethylamino)styrene, acrylamide,methacrylamide, N-methylacrylamide, N-isopropylacrylamide,N-n-butylacrylamide, N-n-octylacrylamide, N,N-dimethylacrylamide,1-vinylimidazole, allylamine, 2,5-distyrylpyridine,2-dimethylaminoethylmethacrylate, N-vinyl-2-pyrrolidone,2-vinyl-2H-indazole, 4-diisopropylamino-l-butene,trans-2-butene-1,4-diamine, 2-vinyl-4,6-diamino-1,3,5-triazine,4-methyl-5-vinylthiazole, N-vinylformamide, N,N-dimethylaminoethylacrylate, N,N-dimethylaminopropylacrylamide, acryloylmorpholine, andN,N-diethylacrylamide.
 13. The adhesive composition according to claim8, wherein the compound capable of forming a compound containing astructure having a lone pair by thermal decomposition is a vulcanizationaccelerator.
 14. The adhesive composition according to claim 8, whereinthe compound capable of forming a compound containing a structure havinga lone pair by thermal decomposition is tetramethylthiuram disulfide.15. The adhesive composition according to claim 5, wherein the compoundC is contained in an amount of 30 to 80 parts by weight based on 100parts by weight of the conjugated diene polymer A.
 16. The adhesivecomposition according to claim 5 or 15, wherein the compound C includesacryloyl- and/or methacryloyl-modified novolak resins.
 17. The adhesivecomposition according to any one of claims 1 to 16, further comprisingat least one additive selected from the group consisting of epoxycompounds, inorganic fillers and high-molecular fillers.
 18. Anultraviolet- or radiation-curable adhesive composition comprising (A) aconjugated diene polymer having a weight-average molecular weight of 500to 100,000, (C) a compound having in its molecule three or morefunctional groups selected from the group consisting of acryloyloxygroup, methacryloyloxy group and groups represented by the followingformula I:

wherein R¹ is C₂-C₅ alkylene group; R² is hydrogen or C₁-C₂ alkyl group;and m is an integer of 0 to 5, and (D) a compound having in its moleculeone or two groups selected from the group consisting of acryloyloxygroup and methacryloyloxy group.
 19. The ultraviolet- orradiation-curable adhesive composition according to claim 18, wherein anend group of the conjugated diene polymer A is selected from the groupconsisting of vinyl group, acryloyl group, methacryloyl group,acryloyloxy group, methacryloyloxy group and allyl group.
 20. Theultraviolet, or radiation-curable adhesive composition according toclaim 18, wherein an end group of the conjugated diene polymer A isacryloyloxy group or methacryloyloxy group.
 21. The ultraviolet- orradiation-curable adhesive composition according to any one of claims 18to 20, wherein the compounds C is contained in an amount of 30 to 80parts by weight and the compound D is contained in an amount 3 to 60parts by weight, each based on 100 parts by weight of the conjugateddiene polymer A.
 22. The ultraviolet- or radiation-curing adhesivecomposition according to any one of claims 18 to 21, further comprisingat least one additive selected from the group consisting of epoxycompounds, inorganic fillers, high-molecular fillers and basiccompounds.
 23. A method for bonding rubber to an adherend, comprising:coating at least a part of a surface of the adherend with the adhesivecomposition as set forth in any one of claims 1 to 22 to form anadhesive layer; optionally irradiating the adhesive layer withultraviolet light or radiation; and vulcanizing an unvulcanized rubberwhile bringing the unvulcanized rubber into press-contact with theadhesive layer, thereby bonding the rubber to the adherend through theadhesive composition.
 24. The method according to claim 23, wherein theadhesive composition as set forth in any one of claims 1 to 17 is usedto form the adhesive layer, and the vulcanization is performed withoutirradiating the adhesive layer with ultraviolet light or radiation. 25.The method according to claim 23, wherein the adhesive composition asset forth in any one of claims 18 to 22 is used to form the adhesivelayer, and the vulcanization is performed after irradiating the adhesivelayer with ultraviolet light or radiation.
 26. The method according toclaim 25, wherein the radiation is electron beam or gamma ray.
 27. Themethod according to any one of claims 23 to 26, wherein the adherend ismade of a plastic material.
 28. The method according to claim 27,wherein the plastic material is selected from the group consisting offilms, fibers, non-woven fabrics, monofilament cords, multifilamentcords and resin molded articles.
 29. The method according to any one ofclaims 23 to 28, wherein the rubber is a diene rubber.
 30. The methodaccording to any one of claims 23 to 29, wherein a vulcanizing agent forthe rubber is sulfur.
 31. The method according to any one of claims 23to 30, wherein the adhesive layer is formed on an undercoat layer whichis formed in advance on at least a part of the surface of the adherend.32. The method according to claim 31, wherein the adhesive layer isformed after irradiating the undercoat layer with ultraviolet light orradiation.
 33. The method according to claim 31 or 32, wherein theundercoat layer is made of an undercoat composition comprising (E) acompound having a bisphenol backbone represented by the followingformula II:

wherein R³ and R⁴ are each independently hydrogen or C₁-C₃ alkyl group;and n is an integer of 1 to 3, and (F) a compound having in its moleculethree or more acryloyloxy group and/or methacryloyloxy group.
 34. Themethod according to claim 33, wherein the undercoat composition containsat least one additive selected from the group consisting of epoxycompounds, inorganic fillers, high-molecular fillers and basiccompounds.
 35. A rubber-reinforcing material produced by the method asset forth in any one of claims 23 to
 34. 36. A rubber article producedusing the rubber-reinforcing material as set forth in claim
 35. 37. Atire produced using the rubber-reinforcing material as set forth inclaim 35.